CN1841191A - Photosensitive thick-film dielectric paste composition and method for making an insulating layer using same - Google Patents
Photosensitive thick-film dielectric paste composition and method for making an insulating layer using same Download PDFInfo
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- CN1841191A CN1841191A CNA2006100733760A CN200610073376A CN1841191A CN 1841191 A CN1841191 A CN 1841191A CN A2006100733760 A CNA2006100733760 A CN A2006100733760A CN 200610073376 A CN200610073376 A CN 200610073376A CN 1841191 A CN1841191 A CN 1841191A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
- C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Gas-Filled Discharge Tubes (AREA)
- Glass Compositions (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Disclosed is a photosensitive thick-film dielectric paste composition that includes a glass frit having a glass softening point not lower than 0 DEG to 40 DEG C below a firing temperature ranging above 450 DEG C and up to 600 DEG C; an organic polymer binder; a photoinitiator; a photocurable monomer; and an organic solvent, wherein the composition is aqueous-developable upon exposure to actinic radiation. A method for forming an insulating layer using the composition is also provided.
Description
Technical field
Present invention relates in general to photosensitive thick-film dielectric paste composition, more specifically to the photosensitive thick-film dielectric paste composition that is used to form the dielectric layer in the electron device.
Background technology
In recent years, two types flat-panel monitor has caused people's very big interest.In one type device (fluorescent emission), between cathode conductor and gate electrode, lay the emitter that electronic emission material is made.Between cathode conductor and gate electrode, apply voltage and make the emitter emitting electrons.Provide the anode electrode of phosphors coating facing to electron emission source.Gate electrode and anode electrode drive with predetermined positive potential, and by this, the electron emission source ejected electron excites phosphorus, cause luminous and demonstration.
In second type device (plasma), on front glass substrate and back glass substrate, form raised areas, as electrode or barrier.Two boards is laid relatively, along peripheral seal and fill with inert gas.Based on picture signal, on electrode, apply voltage, induce (in selected battery) gas discharge, make the phosphorus layer luminous, and cause display image.
Glass thickener be used for the insulating electrode of above-mentioned two types flat-panel monitor.For example, in the fluorescent emission escope,, on substrate, form gate electrode with silver-colored thickener by serigraphy and drying steps.Then, by serigraphy and drying steps, at the dielectric paste of its top formation based on glass, subsequently in 500 ℃-600 ℃, roasting dozens of minutes in the air, thereby the electron emission source of generation field emission type.In plasma display, can on front glass substrate, form silver electrode.This electrode also transparent and form by silver.Be coated with transparent dielectric glass and magnesian dielectric protection layer that glass dust forms on these electrodes.
By transparent rib shape barrier structure is provided, further improve the performance of these devices on transparent dielectric layer.Form transparent rib shape barrier structure by sandblasting leaving the insulation course place.For example, authorize the U.S. Patent number 5 of Wang etc., 985,460 disclose the unsintered tape (green tape) that the rib shape that is used to form plasma display system stops, after the roasting, this unsintered tape forms unbodied non-crystalline glass, wherein the unsintered tape composition comprises basically: (a) inorganic fine powder, and the cumulative volume in this inorganic fine powder comprises the amorphous amorphous glass of (i) 30-60 volume %, the (ii) refractory oxides of 20-70 volume % and the (iii) refractory pigment of 0-50 volume %; Wherein the softening point of glass is than low 50 ℃ at least of 400 ℃ of-650 ℃ of scopes of sintering temperature (better low 100 ℃) of this unsintered tape composition of roasting; (b) has the bonding agent of 40-60 volume % polymkeric substance and 40-60 volume % plastifier.
Still need to be used to form the photosensitive thick-film dielectric paste composition of the dielectric layer in the display device.
Summary of the invention
In one embodiment, provide a kind of photosensitive thick-film dielectric paste composition, contain following component: (a) frit, its glass softening point than greater than 450 ℃ of sintering temperatures to the highest 600 ℃ scopes low 0-40 ℃ or more than; (b) organic polymer binder; (c) light trigger; (d) photocurable monomer; (e) organic solvent, aqueous developable after wherein said composition is exposed in actinic radiation.
In another embodiment, provide a kind of method that forms insulation course in display plate, this method may further comprise the steps: glass substrate is provided; Be coated with this substrate with conductive thick film compositions; This substrate of roasting and electrically conductive composition form electrode; The dielectric paste composition that will contain frit is printed on electrode surface; With actinic radiation the selection area of dielectric combination is carried out the exposure of image mode, to form exposed areas and unexposed zone; Unexposed area develops in aqueous medium; Surpassing 450 ℃ to the highest 600 ℃ temperature ranges, the dielectric paste composition after the roasting exposure, the glass softening point of wherein said frit than sintering temperature low 0 ℃-40 ℃ or more than.
In another embodiment, adopt said method to form insulation course.
In another embodiment, flat-panel monitor comprises above-mentioned composition.
In another embodiment, flat-panel monitor comprises the insulation course that forms according to the method described above.
By following detailed description and claim, other features and advantages of the present invention will be conspicuous.
Embodiment
In one embodiment, provide a kind of photosensitive thick-film dielectric paste composition, comprise following component: (a) frit, its glass softening point than surpass 450 ℃ of sintering temperatures to the highest 600 ℃ scopes low 0-40 ℃ or more than; (b) organic polymer binder; (c) light trigger; (d) photo-curing monomer; (e) organic solvent, aqueous developable after wherein said composition is exposed in actinic radiation.Frit comprises in molar percentage: 66%PbO, 23%SiO
2, 8.5%B
2O
3, 2.5%Al
2O
3Frit also can be unleaded.Said composition can be developed in containing the solution of sodium carbonate.The glass softening point of frit is lower 5 ℃-20 ℃ than sintering temperature.Sintering temperature is 500 ℃-600 ℃, is 520 ℃-540 ℃ in one embodiment.
In another embodiment, provide a kind of method that forms insulation course in display plate, this method may further comprise the steps: glass substrate is provided; Be coated with this substrate with conductive thick film compositions; This substrate of roasting and electrically conductive composition form electrode; The dielectric paste composition that will comprise frit is printed on electrode surface; With actinic radiation the selection area of dielectric combination is carried out the exposure of image mode, form exposed areas and unexposed zone; Unexposed area develops in aqueous medium; At the dielectric paste composition that surpasses after 450 ℃ of temperature range roastings extremely the highest 600 ℃ expose; Wherein the glass softening point of frit than sintering temperature low 0 ℃-40 ℃ or more than.Frit comprises in molar percentage: 66%PbO, 23%SiO
2, 8.5%B
2O
3And 2.5%Al
2O
3Glass dust also can be unleaded.Aqueous medium comprises the solution of 0.4-1.0 weight % sodium carbonate.The glass softening point of frit is lower 5 ℃-20 ℃ than sintering temperature.Calcination steps can be included in 500 ℃ of-600 ℃ of roasting said compositions, also can be 520 ℃ of-540 ℃ of roasting said compositions.After the baking, the thickness of dielectric paste composition can be 20 μ m.
In another embodiment, adopt this method to form insulation course.After the roasting, this layer thickness is 20 μ m.This layer can be transparent.
In another embodiment, flat-panel monitor comprises above-mentioned composition.In another embodiment, flat-panel monitor comprises the insulation course that forms according to the method described above.
Hereinafter will describe a kind of photosensitive thick-film dielectric paste composition in detail, said composition has advantageously solved with dielectric glass laminar surface roughness, visible transmission ratio and has reduced relevant problem with dielectric strength.Use described photosensitive thick-film dielectric paste composition, form pattern by photoetching, roasting subsequently can be formed for the dielectric glass layer in the display device.
Above-mentioned photosensitive thick-film dielectric paste composition forms the dielectric glass layer in being used for when making display device such as flat-panel monitor, promptly adopt photoetching to make said composition form pattern, and roasting forms dielectric layer to carry out sintering then.When the dielectric glass layer that discovery forms at photosensitive thick-film dielectric paste composition of the present invention carried out lithographic patterning, the relation between glass softening point and the baking temperature had influence on the performance of dielectric layer.
For example, when sintering temperature is lower than glass softening point,, thereby cause irregular reflection to visible light because softening inadequate situation makes the surface of dielectric layer become coarse.Under this low sintering temperature condition, in dielectric film, also may there be countless small spaces, cause forming pin hole or other flaw.Because these problems, visible light transmittance in the dielectric layer that makes reduces, and causes that the film flaw of dielectric breakdown has also reduced dielectric strength.
In addition, find when sintering temperature is higher than 40 ℃-80 ℃ of glass softening points, in dielectric layer, to form bubble, thus the transmittance and the dielectric strength of reduction visible light.Under this high-temperature roasting condition (though can realize degas zone completely, forming transparent dielectric layer), the viscosity of dielectric glass descends, and causes shape stability obviously to descend.The high-temperature roasting condition also can promote the reaction with electrode material.Except the constraint that dielectric material is forced, the other problem of existence is that the resolution that can not reach enough when adopting screen printing technique to carry out the pattern printing and contract drawing are than (aspect ratio).
By using sintering temperature 450 ℃-600 ℃ scopes low 0 ℃-40 ℃ or the above frit of softening point than composition, the surface that is provided at the dielectric layer that first step forms is with planarity, can suppress irregular reflection to visible light, to improve the transmittance of visible light, reach the pattern that forms high precision, high-aspect-ratio, for example bubble is minimum to make the coating flaw that brings out dielectric breakdown, improves dielectric strength.
Inorganic component
Frit
For reach sufficient sealing in dielectric layer, in one embodiment, the softening point of frit (Ts) is lower 0 ℃-40 ℃ than sintering temperature, comprises 40 ℃, and in another embodiment, the softening point of frit is lower 5 ℃-20 ℃ than sintering temperature, comprises 20 ℃.The example of DEFORMATION POINTS is, glass substrate is 600 ℃, and soda-lime glass is 540 ℃.Therefore, baking temperature can be between the volatilization point of the used organic bond of the DEFORMATION POINTS of one of aforesaid substrate and said composition.If find to take place under the temperature that is lower than 400 ℃ of-450 ℃ of scopes softening, the organic component that produces at calcination steps is trapped in the dielectric film, forms bubble or owing to carbonization is easy to blackening in dielectric layer.
In one embodiment, frit comprise the lead borosilicate glass material, contain bismuth, the borate glass material of cadmium or alkaline earth metal compound such as barium or calcium.The production of frit can relate to following steps, and for example the oxide with above-mentioned element dissolves with glass ingredient, and these materials are poured in the water, forms frit solution.This batch ingredients can be the material that required oxide can be provided under conventional frit formation condition.For example, boron oxide can derive from that boric acid, silicon dioxide can derive from flint, baryta can derive from barium carbonate.In another embodiment, frit does not contain any plumbous component.In the weight of total composition, the proper content of frit is 30-80 weight %.
Glass grinds with water in vibromill, reduces the granularity of frit, and the frit of basic uniform particle size is provided.Be gathered into piece because prevent solid constituent, frit can be removed big particle by dusting cover.To the suitable surface area/weight ratio of frit and granularity for being not more than 10m
2/ g, and 50% particle diameter (d
50) be 0.6-2.0 μ m.
May disturb cleaning to decompose the inorganic material of (clean decomposition) owing to have the easy absorption of granule of high surface, in addition, in above-mentioned granularity and surface area, be the d of 0.8-1.2 μ m
50Be particularly useful.In addition, greater than the d of 0.8-1.2 μ m
50Granularity can reduce sintering character.
Inorganic additive
In an embodiment of the dielectric layer that need not transparent characteristic, available inorganic powder is made filler.The example of suitable inorganic powder comprises aluminium and silicon dioxide.
Organic component
Organic vehicle
Organic vehicle is to be used for the solid dispersed of the fine grinding of composition is become to be easy to be applied to the medium of the form on glass or other suitable substrate.Therefore, organic vehicle must at first can make above-mentioned Pickering ground be scattered in wherein.Secondly, the rheological properties of this organic vehicle must can give this dispersion good be coated with feature.
When dispersion formed film, the organic vehicle that wherein is dispersed with frit (inorganic bond) included, but is not limited to: volatile organic solvent, polymer adhesive, monomer and initiating agent.Organic vehicle also can comprise other material, for example plastifier, separant, spreading agent, remover, scale inhibitor and wetting agent.
For obtaining dispersion completely, the solvent composition (can be the potpourri of multiple solvent) of organic vehicle is selected, so that under atmospheric pressure use lower heat, organic solvent can be evaporated from dispersion.In addition, seethe with excitement under the temperature that the boiling point of solvent other adjuvant that must comprise in than organic vehicle and decomposition temperature are enough low.Can use suitably that boiling point is lower than 150 ℃ suitable solvent under the atmospheric pressure.The example of suitable solvent comprises: benzene, acetone, dimethylbenzene, ethanol, methyl ethyl ketone, 1,1,1-trichloroethanes, zellon, pentyl acetate, 2,2,4-triethyl pentanediol-1,3-one isobutyrate, toluene, methylene chloride, ethylene glycol monoalkyl ether, for example glycol monomethyl-just-propyl ether and ethylene glycol bisthioglycolate alkyl ether.For with composition curtain coating film forming, methylene chloride is because its volatility is especially suitable.
Also can comprise the plastifier that one or more are used for reducing polymer adhesive Tg in the organic vehicle.Add plastifier and help to guarantee good stepped construction with base material, and improve the development capability of the unexposed area of composition.Yet,, should use plastifier less for reducing the organic amount that must remove during by the film of composition curtain coating in roasting as far as possible.The selection of suitable plasticizers is mainly by the polymer adhesive decision of selecting.
Can comprise by suitably used plastifier: diethyl phthalate, dibutyl phthalate, butyl benzyl phthalate, dibenzyl phthalate, alkylphosphonate, poly alkylene glycol, glycerine, poly-(oxirane), hydroxyethylated alkylphenol, tricresyl phosphate, triethylene-glycol diacetate (triethyleneglycol diacetate) and polyester.Dibutyl phthalate can effectively and with low concentration use in the acrylate copolymer system.
Photosensitive composition of the present invention also can cover the form of the photoresists layer of base membrane layer and use.Photosensitive composition can be coated on the base membrane layer of support, its amount should be able to make dry coating thickness reach 0.001 inch (about 0.0025cm)-0.01 inch (about 0.025cm).Can from various types of films, select temperature variation is had the suitable basement membrane of high-dimensional stability, comprise, for example the film made of polyamide, polyolefin, polyester, polyvinyl and cellulose esters by high molecular weight polymers.The thickness of base membrane layer can be 0.005 inch (about 0.0013cm)-0.008 inch (about 0.2cm) or thicker.
Adhesion when preventing to preserve with web-like between resist layer and the base membrane layer surface, available removable emulsion sheet is protected described resist layer.Can select the suitable removable sheet that covers from the similar heavy polymer film that is used for above-mentioned base membrane layer, and describedly cover the thickness that sheet can have similar wide region.Suitable used thickness is that the tygon of 0.001 inch (about 0.0025cm) covers sheet.The basement membrane of above-mentioned support and cover sheet and provide photoresists layer excellent protection storing and use between early stage.
Carry out between exposure period in the pattern mode,, can use removable support membrane to protect this base membrane layer for preventing to be layered in photosensitive layer on the base membrane layer and the adhesion between the exposure tool.If exposed before removable support membrane is removed, support membrane must be able to make most of irradiation actinic light thereon pass through.The proper supporting film comprises that thickness is about the transparent polyethylene terephthalate film of 0.001 inch (about 0.0025cm).
When not providing removable when covering sheet and resist layer and storing, for preventing and the adhesion of photoresists layer, can be coated with a kind of material, the thin peel ply of making as wax or silicone at the back side of strippable base membrane layer with web-like.Perhaps, can carry out flame treatment or discharge process, increase the viscosity of photosensitive coating by the stayed surface that need are covered.
The weight ratio of inoganic solids and organic component is 2.0-6.0, also can be 2.6-4.5.For obtaining sufficient dispersiveness and rheological properties, require this ratio to be not more than 6.0.Yet this ratio is less than 2.5 o'clock, the quantitative change De Taigao of organic component that must burn off, thereby the quality that jeopardizes final coating.The ratio of inoganic solids and organic component depends on granularity, the organic component of inoganic solids, depends on that also the surface preparation of inoganic solids is handled.
When particle is handled with organo silane coupling agent, can improve the ratio of inoganic solids and organic component.Yet minimum for the flaw that makes roasting, the preferred use hanged down the organic component of measuring.The preferred use among the present invention corresponding to general formula R Si (OR ')
3Those organosilane.In the formula, R ' is methyl or ethyl, R can be selected from methacryloxypropyl (methacryloxypropyl), polyalkylene oxide and other can with the interactional organo-functional group of the organic substrate of film.
When dispersion is coated with the thick film paste composition, can use suitable thick film organic vehicle and suitable rheology control agent or low voc solvent.When composition was mixed with the thick film paste composition, conventional coating process comprised serigraphy.Therefore, composition must have suitable viscosity and can easily pass through silk screen.Though when compositions formulated, will consider rheological characteristics, but also to consider following factor, with the thorough wetting solid of organic vehicle, acceptable rate of drying, coated substrate, provide enough dry film intensity to bear violent processing and good roasting (fireability).The satisfactory appearance of composition (when roasting) also is the feature of requirement.
According to above standard, the suitable inert fluid that can utilize wide region is as organic vehicle.Many organic vehicles that are used for thick film combination comprise the resin that is dissolved in solvent formation solution.The boiling point of suitable solvent is 130 ℃ of-350 ℃ of scopes.
The resin that is particularly useful for this purpose is the single-butyl ether of the acid moieties of the polymethacrylate of lower alcohol and diethylene glycol monoacrylate.The solvent that also can be used for the thick film coating comprises terpenes, α-and β-terpilenol for example, the potpourri of these materials and other solvent, described other solvent are for example kerosene, dibutyl phthalate, butyl carbitol, butyl carbitol acetate ester, hexanediol and high boiling alcohol or alcohol ester.Prepare the various combinations of these solvents and other solvent, obtain to be coated with required appropriate viscosity and volatility.Therefore, last composition can be thixotropic, perhaps can have newton's feature according to adjuvant contained in the composition.
Organic vehicle in the dispersion and the ratio of inoganic solids can be according to the types of the method for coating dispersion and used organic vehicle and are had obviously different.For reaching good coating, dispersion generally comprises complementary amount, i.e. 50-90 weight % solid and 50-10 weight % organic vehicle.The dispersion of the type generally is the semifluid that is called the viscosity of " thickener ".
Easily make this thickener with the triple-roller mill function.The range of viscosities of thickener generally is lower than the viscosity during the measurement.The amount of used organic vehicle and type are mainly determined by the required ultimate density of preparation and the print thickness of selection.
The waterborne polymeric bonding agent
According to the resinous principle of selecting in the organic component, but but but waterborne polymeric bonding agent broad sense is divided into alkali treatment and bonding agent water treatment.But the polymer adhesive of alkali treatment is the acrylic acid C that contains ethylenic unsaturated carboxylic acid site
1-10Arrcostab or methacrylic acid C
1-10The multipolymer of Arrcostab or interpretation.This site accounts at least 16% of polymer weight, preferred 20-30%.Carboxylic acid comprises the ethylenic unsaturated monocarboxylic, for example acrylic acid, methacrylic acid and butenoic acid; Ethylenic unsaturated dicarboxylic, for example fumaric acid, itaconic acid, citraconic acid, vinyl succinic acid and maleic acid; And half ester and, if suitable can be the potpourri of acid anhydride or above material.Because methacrylate polymer burn off more cleanly in low-oxygen environment is than acrylate copolymer preferable methyl acrylate copolymer.
In the scope of above-mentioned nonacid comonomer, in the embodiment, alkyl acrylate or alkyl methacrylate account at least 70 weight % of polymkeric substance, account at least 75 weight % in another embodiment.
As long as can satisfy above-mentioned composition requirement and following physical condition, the alkyl acrylate or the alkyl methacrylate part of the alternative polymkeric substance of non-carboxylic moiety of polymer adhesive, non-carboxylic moiety can comprise other non-acrylic acid and the non-acid comonomer that reaches 50 weight %, for example styrene, vinyl cyanide, vinyl acetate, acrylamide and acrylic-amino Arrcostab or amino alkyl methacrylate.Yet, since the more very difficult this monomer that burnouts fully, the therefore preferred this monomer that is no more than 25 weight % that uses.
Handle above acrylic acid and methacrylate polymer, also can use various polyolefin, include, but is not limited to tygon, polypropylene, polyisobutylene and ethylene-propylene copolymer.Also can use the polyethers of the polymkeric substance that is rudimentary alkylene oxide, for example polyethylene oxide.
But the binder polymer of operable water treatment comprises water-soluble cellulose derivative, for example hydroxyethyl cellulose, HEMC and hydroxypropyl cellulose.
The photocurable monomer
The photocurable component comprises the addition polymerizable unsaturated monomer compound with at least one polymerisable ethylenic unsaturated group.Described monomeric compound can form high molecular weight polymers by the chain growth addition polymerization that free radical causes.These monomeric compounds are on-gaseous, and promptly their normal boiling point is higher than 100 ℃, and organic polymer binder is had plasticization.
Be fit to use separately or comprise: tert-butyl acrylate and metering system tert-butyl acrylate with monomer that other combination of monomers is used, acrylic acid 1,5-pentadiol ester and methacrylic acid 1, the 5-pentadiol ester, acrylic acid N, N-dimethylamino ethyl ester and methacrylic acid N, the N-dimethylamino ethyl ester, ethylene glycol diacrylate and Ethylene glycol dimethacrylate, diacrylate 1,4-butanediol ester and dimethacrylate 1, the 4-butanediol ester, diacrylate diglycol ester and dimethacrylate diglycol ester, hexanediol diacrylate and dimethacrylate hexanediol ester, diacrylate 1, ammediol ester and dimethacrylate 1, the ammediol ester, diacrylate decanediol ester and dimethacrylate decanediol ester, diacrylate 1,4-cyclohexanediol ester and dimethacrylate 1,4-cyclohexanediol ester, 2,2-dihydroxy methylpropane diacrylate and 2,2-hydroxymethyl-propane dimethylacrylate, glycerol diacrylate and dimethyl allene acid glyceride, diacrylate tripropylene glycol ester and dimethacrylate tripropylene glycol ester, three acrylic acid glyceride and trimethyl acrylic acid glyceride, trimethylolpropane triacrylate and trimethylol-propane trimethacrylate, pentaerythritol acrylate or pentaerythrite methacrylate, the trimethylolpropane triacrylate of polyoxyethyleneization and the trimethylol-propane trimethacrylate of polyoxyethyleneization and U.S. Patent number 3,380,831 disclosed similar compounds; 2,2-two (right-hydroxy phenyl) diacrylate, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, 2,2-two (right-hydroxy phenyl) propane dimethylacrylate, the diacrylate triethyleneglycol ester, polyoxy ethyl-2,2-two-(right-hydroxy phenyl) propane dimethylacrylate, two of bisphenol-A-(3-methacryloxy-2-hydroxypropyl) ether, two of bisphenol-A-(2-methacryloxyethyl) ether, two of bisphenol-A-(3-acryloxy-2-hydroxypropyl) ether, two of bisphenol-A-(2-acryloxy ethyl) ether, 1, two of 4-butylene glycol-(3-methacryloxy-2-hydroxypropyl) ether, the dimethacrylate triethyleneglycol ester, the polyoxyethyl propyl trimethylolpropane triacrylate, diacrylate butanediol ester and tetramethylene dimethacrylate, three acrylic acid 1,2,4-butantriol ester and trimethyl acrylic acid 1,2,4-butantriol ester, diacrylate 2,2,4-trimethyl-1,3-pentadiol ester and dimethacrylate 2,2,4-trimethyl-1, the 3-pentadiol ester, dimethacrylate 1-phenyl-1, the 2-ethyl, diallyl fumarate, styrene, dimethacrylate 1,4-Benzenediol ester, 1,4-di isopropenylbenzene and 1,3,5-three isopropenylbenzenes.Also can use molecular weight to be at least 300 ethylenically unsaturated compounds, for example by the aklylene glycol of 2-15 carbon or the diacrylate alkylene ester or the diacrylate polyalkylene glycols ester of the polyalkylene ether ethylene glycol of 1-10 ehter bond are arranged, U.S. Patent number 2,927,022 disclosed compound, the compound of key that for example has the ethylenic unsaturated link, particularly end group of a plurality of interpolations.
Preferred monomer comprises the ethylating trimethylolpropane triacrylate of polyoxy, ethylating pentaerythritol triacrylate, dipentaerythritol monohydroxy five acrylate and dimethacrylate 1,10-decanediol ester.In the general assembly (TW) of dried photopolymerization coating, the amount of monomer is 6-45 weight %.
Light trigger
Suitable light trigger is included in replacement or the unsubstituted many ring quinones that has ring carbon in two in the carbocyclic ring system of conjugation, for example 9, the 10-anthraquinone, 2-methylanthraquinone, the 2-EAQ, 2-tert-butyl group anthraquinone, the prestox anthraquinone, 1, the 4-naphthoquinones, 9, the 10-phenanthrenequione, benzanthrene-7, the 12-diketone, 2,3-aphthacene-5,12-diketone, the 2-methyl isophthalic acid, the 4-naphthoquinones, 1,4-dimethyl anthraquinone, 2,3-dimethyl anthraquinone, 2-phenyl anthraquinone, 2,3-diphenyl anthraquinone, invite quinone, 7,8,9,10-tetrahydrochysene aphthacene-5,12-diketone and 1,2,3,4-tetrahydro benzo anthracene-7,12-diketone.U.S. Patent number 2,760,863 have mentioned other useful light trigger (is thermoactive though some are arranged) when the temperature that is lower than 85 ℃, comprise company-keto-aldehyde alcohol (vic-ketoaldonyl alcohol), for example benzoin and new penta acyloin (pivaloin); Acyloin ether, for example benzoin methyl ether and benzoin ethylether; The aromatics acyloin of α-hydrocarbon-replacement, for example α methylbenzene acyloin, α-allyl benzene acyloin and α-phenyl benzoin.U.S. Patent number 2,850,445,2,875,047,3,097,096,3,074,974,3,097,097 and 3,145, but 104 mentioned the dyestuff and the reductive agent of photo-reduction; And the dyestuff of azophenlyene, piperazine and the peaceful class of quinoline.For example, U.S. Patent number 3,427,161,3,479,185 and 3,549,367 mention comprise Michler's keton, benzophenone, 2,4, the leuco dye and their potpourri of 5-triphenyl imidazole radicals dimer and hydrogen donor (comprising leuco dye) also can be used as initiating agent.U.S. Patent number 4,162,162 disclose also the photosensitizer that can use with light trigger.In the general assembly (TW) of dried photopolymerization coating, the amount of light trigger is 0.05-10 weight %.
Spreading agent
Spreading agent is used to guarantee that dead matter are fully wetting by organic polymer and monomer.When preparation has the thickener of photoactivation of good serigraphy and the levelability and the characteristic that burnouts, require dead matter to disperse fully.The effect of spreading agent is to make polymer adhesive combine with inoganic solids, or makes it moistening inoganic solids, so that the system of no aggressiveness to be provided.Suitable spreading agent is included in the H.L.Jacubauskas work, " A-B blocking-up multipolymer is as the purposes (The Use of A-B Block Copolymers asDispersants for Nonaqueous Coating Systems) of the spreading agent of non-aqueous coating system ", Journal of Coating Technology, the 58th volume, No. 736, the A-B spreading agent of describing in the 71-82 page or leaf.Other useful A-B spreading agent is at U.S. Patent number 3,684,771,3,788,9984,070,388 and 4,032,698 with British Patent No. 1,339,930 in describe.
As long as photopolymerisable compositions can keep its desirable characteristics, the photosensitive thick film dielectric paste composition can contain a small amount of other composition, comprises pigment, dyestuff, thermal polymerization, tackifier (as organo silane coupling agent), plastifier and coating additive (for example polyethylene oxide).In the weight of inorganic particle, the organosilane amount that is particularly useful can reach 3.0 weight %.The particle handled needs less organism, thereby can reduce the amount of organic vehicle in the composition, makes easier burn off in roasting process.Organosilane has also improved dispersibility, can allow lower inorganic bond and solid ceramic ratio under same sealing.
Handle
Photosensitive thick-film dielectric paste composition can be the form that is applied to the film on the base material, or with the form of the thickener method by conventional formation coating, for example serigraphy is applied on the base material.
Use the film of photosensitive thick-film dielectric paste composition to form in the following manner,, and heat this cast layer and therefrom remove volatile organic solvent at flexible substrate top casting one layer composition thin layer.In addition, solvent-free layer can separate from base material.Film or paste composition can be used for forming insulation course used in the flat-panel monitor.When forming coating by method for printing screen, printing and drying steps can repeat for several times, to obtain required build.
Select for use to have the rate that is coated with out more greatly the sieve of (coat-out rate) helps forming dielectric layer, for example make, and size of mesh is the sieve of 150-250 with the SUS stainless steel.As long as having good uniformity on the face can be carried out drying by hot-air or infrared system.Drying condition also depends on the film thickness of printing.The condition that can obtain inviscid dry film is, for example 80-100 ℃, and 10-20 minute.Then, the dielectric combination of photopolymerization carries out the exposure of pattern mode with actinic radiation, thereby forms exposure region and unexposed area.The system that use can be sent ultraviolet light exposes, and this system uses high pressure mercury vapour lamp or ultra high pressure mercury mercury vapo(u)r lamp as light source.Can be at 50-400mJ/cm
2Exposure energy (@365nm) carries out drying, although this also depends on dielectric combination and film thickness.Remove by the method for developing the unexposed area of this layer.
Carrying out removing the not part of radiant exposure in the process of water-based development with the aqueous solution that contains 0.4-1.0 weight % sodium carbonate, and the exposed portion maintenance is unaffected basically.The development number of times generally is the number of times that is used for developing fully.Can use transmission type developing machine or develop by the immersion method with nozzle.In transmission type toning system, development time generally be tens seconds to a few minutes.Before baking operation, also other treatment step be can carry out, organic component and sintering inorganic bond (frit) removed by volatilization subsequently.Sintering temperature is subjected to the restriction of other component.For using the plasma display panel-Field Emission Display (PDPFED) of glass substrate, carry out sintering 500-600 ℃ (maximum temperature) usually.Composition can be in the environmental air roasting of essentially no oxygenant.
Following examples have further described the present invention, and these embodiment only are illustrative, the claims of the present invention scope are not construed as limiting.
Embodiment
Embodiment 1 and 2
Unless note is arranged in addition, all parts and percentages all are to be benchmark with weight in following examples, and all temperature are degree centigrade.
Dead matter
Frit: in water, be ground to particle size range d
50Be the 0.8-1.2 micron.
The lead borosilicate glass of doing (embodiment 1):
Form (component mol%): PbO (66), SiO
2(23), B
2O
3(8.5), Al
2O
3(2.5)
Glass softening point=525 ℃
Borosilicate glass (embodiment 2):
Form (component mol%): SiO
2(7.1), Al
2O
3(2.1), B
2O
3(8.4), CaO (0.5), ZnO (12.0), Bi
2O
3(69.9)
Glass softening point=537 ℃
Organic component
Polymer adhesive: the multipolymer of 75% methyl methacrylate and 25% methacrylic acid; M
w=6,000; Tg=136 ℃; Acid number: 160
Solvent: TEXANOL (single isobutyric acid 2,2,4-trimethyl-1,3-pentadiol ester)
Monomer: TEOTA 1000 (the trihydroxy methyl third no triacrylate of polyoxyethyleneization; M
w=1,162)
Initiating agent: EMK: ethyl Michler's keton
BP: benzophenone
Antioxidant: BHT (butylated hydroxy-methylbenzene)
Stabilizing agent
The preparation dielectric paste composition
A. prepare organic vehicle:
Organic component (solvent and polymer adhesive) heats and mixes in 135 ℃.Continue heating and stirring, form solution until the polymer adhesive dissolving.Solution is cooled to 100 ℃, adds initiating agent and stabilizing agent then.The potpourri that stirring obtains dissolves until solid constituent, makes potpourri pass through one 400 also cooling of purpose filter then.
B. prepare dielectric inorganic material-frit:
In the Sweco grinding machine, be 0.5 inch, grow 0.5 inch aluminium oxide cylinder with diameter, 8 kilograms of frit Ferro 3467 and 8 premium on currency were ground 16 hours, reach the d of 2.3-2.7 micron
50Size-grade distribution.This frit-aqueous mixtures is by 400 purpose sieves, and by S.G.Frantz 241F2 type magnetic separator, this separation vessel is set 30 amperes of operations down at 11.5V DC.
Then, use Virtis Console 12 freeze driers, freeze drying frit potpourri.Adopt this technology to remove all water and generally need 3 days.
C. prepare thickener
Prepare dielectric paste by under gold-tinted, in mixer, mixing organic vehicle, monomer and spreading agent.Add frit then, stirred this potpourri 30 minutes.The mixture ageing that obtains 12 hours uses three-roll mill then, carries out the roller mill with the 400psi roller pressure.Be complete blend compositions, will make composition just can reach abundant mixing 5 times usually by this grinding machine.Paste composition sieves by 400 purpose sieves then.
Add TEXANOL, the viscosity of thickener transfers to 120P.S. from 20P.S. with this moment.This range of viscosities is best serigraphy viscosity.
Below be by weight percentage the amount of each component in the above-mentioned prescription:
Embodiment 1 embodiment 2
Frit: lead borosilicate glass 50.0 weight % borosilicate glasses: 62.5 weight %
Polymer adhesive: 10.0 weight %, 7.50 weight %
Reaction monomers: 6.0 weight %, 4.50 weight %
Initiating agent: 2.0 weight %, 1.50 weight %
Stabilizing agent: 0.01 weight %, 0.0 weight %
Solvent: 31.99 weight %, 24.0 weight %
The photosensitive glass paste composition of embodiment 1 is through printing, drying, exposure and developing process, and the figuratum glass thickener that makes after the roasting.The shape of visual inspection sample and transparency.The representative part preparation in the following manner of the voltage resistance characteristic of the present composition: adopt serigraphy, with Fodel
TMThe AG conductor of DC206 Photoimageable (E.I.du Pont de Nemours and Company, Wilminton, DE) deposit on the glass substrate of soda-lime glass, and preparation size is 1cm * 4cm, thickness is lower floor's conductive pattern of 6 μ m after 530 ℃ of dryings and the roasting, preparation dried thickness after 530 ℃ of roastings is the dielectric layer of 20 μ m, in addition, but Ag thickener K3714 (E.I.du Pont de Nemours andCompany with the serigraphy roasting, Wilminton, DE), 430 ℃ of roastings, to come preparation size be 1mm * 4mm and peel off patterned electrodes perpendicular to the top layer of lower floor's conductive pattern.The voltage resistance of measuring the dielectric layer in the representative part is 1500V.
Similar shown in the characteristic of the lead-free composition example of embodiment 2 and the table 1.
Table 1
| Sintering temperature (℃) | |||||
| 490 | 530 | 550 | 560 | 590 | |
| The shape of dielectric layer after the roasting | Non-trapezoidal | Square is to trapezoidal | Trapezoidal | Trapezoidal | Floating |
| Transparency | Muddy | Clear | Clear | Clear | Muddy |
Unless otherwise defined, all technology used herein and scientific terminology all with the same meaning of those of ordinary skill in the art's common sense.Though similarly or be equivalent to method as herein described and material can be used for implementing or test the present invention, at this paper suitable method and material have been described.If any conflict,, comprise that definition is as the criterion with this instructions.In addition, material, method and embodiment only are illustratives and nonrestrictive.
Claims (13)
1. photosensitive thick-film dielectric paste composition comprises following component:
(a) frit, its softening point is no more than 0-40 ℃ than hanging down above 450 ℃ of firing temperatures to the highest 600 ℃ of scopes;
(b) organic polymer binder;
(c) light trigger;
(d) photo curable monomer and
(e) organic solvent;
Described composition is an aqueous developable after exposing with actinic radiation.
2. composition as claimed in claim 1 is characterized in that, in molar percentage, described frit contains 66%PbO, 23%SiO
2, 8.5%B
2O
3, 2.5%Al
2O
3Potpourri, or lead-free mixture.
3. the described composition of each claim as described above is characterized in that described composition can develop in containing the solution of sodium carbonate.
4. the described composition of each claim as described above is characterized in that, low 5 ℃-20 ℃ of the firing temperature of the glass softening point of described frit than 500 ℃-600 ℃.
5. method that forms the insulation course in the display plate, this method may further comprise the steps:
(a) provide glass substrate;
(b) be coated with this substrate with conductive thick film compositions;
(c) fire the substrate and the electrically conductive composition of step (b), form electrode;
(d) dielectric paste composition that will contain frit is printed on the electrode surface of step (c);
(e) with actinic radiation the selection area of the dielectric combination of step (d) is carried out the exposure of pattern mode, form exposure region and unexposed area;
(f) develop in aqueous medium in the unexposed area that step (e) is formed; With
(g) surpassing 450 ℃ to the highest 600 ℃ temperature, firing the dielectric paste composition after the exposure of step (f), the glass softening point of described frit is no more than 0 ℃-40 ℃ than firing temperature is low.
6. method as claimed in claim 5 is characterized in that, in molar percentage, described frit contains 66%PbO, 23%SiO
2, 8.5%B
2O
3, 2.5%Al
2O
3Potpourri, or lead-free mixture.
7. as claim 5 or 6 described methods, it is characterized in that described aqueous medium comprises the solution of 0.4-1.0 weight % sodium carbonate.
8. as each described method among the claim 5-7, it is characterized in that the glass softening point of described frit is lower 5-20 ℃ than firing temperature, and described firing temperature is 500 ℃ of-600 ℃ of scopes.
9. as each described method among the claim 5-8, it is characterized in that the thickness of described dielectric paste composition after step (g) is fired is 20 μ m.
10. an insulation course adopts each described method formation among the claim 5-9.
11. insulation course as claimed in claim 10 is characterized in that, the thickness of this layer after firing step is 20 μ m, or this coating is transparent.
12. a flat-panel monitor comprises composition as claimed in claim 1.
13. a flat-panel monitor that comprises insulation course, described insulation course forms according to each described method among the claim 5-8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/096,464 US20060223690A1 (en) | 2005-04-01 | 2005-04-01 | Photosensitive thick-film dielectric paste composition and method for making an insulating layer using same |
| US11/096,464 | 2005-04-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1841191A true CN1841191A (en) | 2006-10-04 |
Family
ID=36676524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006100733760A Pending CN1841191A (en) | 2005-04-01 | 2006-03-31 | Photosensitive thick-film dielectric paste composition and method for making an insulating layer using same |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20060223690A1 (en) |
| EP (1) | EP1708024A2 (en) |
| JP (1) | JP2006313324A (en) |
| KR (1) | KR100768647B1 (en) |
| CN (1) | CN1841191A (en) |
| TW (1) | TW200642980A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442782A (en) * | 2011-09-30 | 2012-05-09 | 南京华显高科有限公司 | Glass powder slurry with photosensitive characteristic |
| CN103760751A (en) * | 2013-12-20 | 2014-04-30 | 深圳市查科本显示材料有限公司 | High-temperature yellowing resistant and high-temperature high-humidity resistant OC negative photoresist and process method thereof in manufacturing of touch screen device |
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|---|---|---|---|---|
| WO2008038544A1 (en) | 2006-09-28 | 2008-04-03 | Jsr Corporation | Method for resist lower layer film formation, composition for resist lower layer film for use in the method, and method for pattern formation |
| JP2008269863A (en) * | 2007-04-18 | 2008-11-06 | Matsushita Electric Ind Co Ltd | Manufacturing method of plasma display panel |
| CN101939811A (en) * | 2007-12-21 | 2011-01-05 | E.I.内穆尔杜邦公司 | Resinates containing acqueous developable photoimageable carbon nanotube pastes with enhanced performance |
| US20110094579A1 (en) * | 2009-10-26 | 2011-04-28 | Yukika Yamada | Electrode substrate, method of preparing same, and photoelectric conversion device including same |
| JP2011091012A (en) * | 2009-10-26 | 2011-05-06 | Samsung Sdi Co Ltd | Electrode substrate, method of manufacturing the same, and photoelectric conversion element |
| US8586660B2 (en) * | 2010-04-07 | 2013-11-19 | Samsung Electronics Co., Ltd. | Dielectric paste composition, method of forming dielectric layer, dielectric layer, and device including the dielectric layer |
| JP6024147B2 (en) * | 2011-03-30 | 2016-11-09 | 東レ株式会社 | Dielectric paste, and method for manufacturing substrate on which dielectric layer and barrier rib are formed using the same |
| WO2018037729A1 (en) * | 2016-08-26 | 2018-03-01 | 株式会社村田製作所 | Photosensitive glass paste, electronic component, and method for manufacturing electronic component |
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| US4959295A (en) * | 1988-05-31 | 1990-09-25 | E. I. Du Pont De Nemours And Company | Process of making a photosensitive semi-aqueous developable ceramic coating composition |
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| US6197480B1 (en) * | 1995-06-12 | 2001-03-06 | Toray Industries, Inc. | Photosensitive paste, a plasma display, and a method for the production thereof |
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-
2005
- 2005-04-01 US US11/096,464 patent/US20060223690A1/en not_active Abandoned
-
2006
- 2006-03-17 EP EP06005511A patent/EP1708024A2/en not_active Withdrawn
- 2006-03-28 TW TW095110621A patent/TW200642980A/en unknown
- 2006-03-31 KR KR1020060029263A patent/KR100768647B1/en not_active IP Right Cessation
- 2006-03-31 CN CNA2006100733760A patent/CN1841191A/en active Pending
- 2006-04-03 JP JP2006102207A patent/JP2006313324A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442782A (en) * | 2011-09-30 | 2012-05-09 | 南京华显高科有限公司 | Glass powder slurry with photosensitive characteristic |
| CN103760751A (en) * | 2013-12-20 | 2014-04-30 | 深圳市查科本显示材料有限公司 | High-temperature yellowing resistant and high-temperature high-humidity resistant OC negative photoresist and process method thereof in manufacturing of touch screen device |
| CN103760751B (en) * | 2013-12-20 | 2018-05-25 | 深圳市查科本显示材料有限公司 | High-temperature yellowing resistant and high-temperature high-humidity resistant OC negative photoresist and process method thereof in manufacturing of touch screen device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100768647B1 (en) | 2007-10-18 |
| EP1708024A2 (en) | 2006-10-04 |
| US20060223690A1 (en) | 2006-10-05 |
| JP2006313324A (en) | 2006-11-16 |
| TW200642980A (en) | 2006-12-16 |
| KR20060105624A (en) | 2006-10-11 |
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